[go: up one dir, main page]

EP4407002A1 - Composition élastomère réticulable et article moulé en caoutchouc fluoré - Google Patents

Composition élastomère réticulable et article moulé en caoutchouc fluoré Download PDF

Info

Publication number
EP4407002A1
EP4407002A1 EP24169936.2A EP24169936A EP4407002A1 EP 4407002 A1 EP4407002 A1 EP 4407002A1 EP 24169936 A EP24169936 A EP 24169936A EP 4407002 A1 EP4407002 A1 EP 4407002A1
Authority
EP
European Patent Office
Prior art keywords
mass
plasma
group
less
fluorine
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP24169936.2A
Other languages
German (de)
English (en)
Inventor
Seiichi Hirano
Tsuyoshi Noguchi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Daikin Industries Ltd
Original Assignee
Daikin Industries Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=66174063&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=EP4407002(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Application filed by Daikin Industries Ltd filed Critical Daikin Industries Ltd
Publication of EP4407002A1 publication Critical patent/EP4407002A1/fr
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C08K3/14—Carbides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/12—Compositions of unspecified macromolecular compounds characterised by physical features, e.g. anisotropy, viscosity or electrical conductivity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
    • C08K2003/3009—Sulfides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/16—Halogen-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Definitions

  • the invention relates to crosslinkable elastomer compositions and fluoroelastomer molded articles.
  • compositions constituting such a member are a composition containing a crosslinkable fluorine-containing elastomer and SiO 2 as disclosed in Patent Literature 1.
  • Another example thereof is a composition containing a crosslinkable fluorine-containing elastomer and silicon carbide particles having a bulk density of 0.15 g/cm 3 or less as disclosed in Patent Literature 2.
  • the invention aims to provide a crosslinkable elastomer composition having a small weight reduction percentage and amount of particles generated after plasma irradiation under specific conditions and a small compression set at high temperature.
  • the invention relates to a crosslinkable elastomer composition including a crosslinkable elastomer and a surface-oxidized non-oxide ceramic filler.
  • the non-oxide ceramic filler is preferably silicon carbide.
  • the non-oxide ceramic filler preferably has an average particle size of 0.1 um or smaller.
  • the crosslinkable elastomer is preferably a copolymer of tetrafluoroethylene and perfluoro(alkyl vinyl ether).
  • the invention also relates to a fluoroelastomer molded article having a weight reduction percentage of 2.5% by mass or less and an amount of particles generated of 0.05% by mass or less after O 2 plasma irradiation under the following conditions, a weight reduction percentage of 1.8% by mass or less and an amount of particles generated of 0.05% by mass or less after NF 3 plasma irradiation under the following conditions, and a compression set of 50% or less after aging at 300°C for 70 hours, the conditions being: Sample: O-ring (AS-568A-214)
  • the crosslinkable elastomer composition of the invention containing a surface-oxidized non-oxide ceramic filler, can simultaneously achieve a small weight reduction percentage and amount of particles generated after plasma irradiation (plasma resistance) and a small compression set at high temperature (heat resistance).
  • the crosslinkable elastomer composition of the invention contains a crosslinkable elastomer and a surface-oxidized non-oxide ceramic filler.
  • the filler may not be completely surface-oxidized and may be partially surface-oxidized.
  • the surface-oxidation state can be determined by electron spectroscopy for chemical analysis (ESCA).
  • ESCA enables elemental analysis of a site about 3 to 5 nm deep from the surface of a particle, and thus can determine whether the surface of the filler is oxidized or not.
  • non-oxide ceramic filler examples include, but are not limited to, a carbide, a silicide, a sulfide, and a fluoride.
  • the carbide include titanium carbide, boron carbide, zirconium carbide, hafnium carbide, tantalum carbide, tungsten carbide, niobium carbide, and silicon carbide.
  • the silicide examples include titanium silicide, molybdenum silicide, and zirconium silicide.
  • the sulfide examples include tungsten sulfide and molybdenum disulfide.
  • the fluoride include aluminum fluoride, yttrium fluoride, and barium fluoride. In order to simultaneously achieve a small weight reduction percentage and amount of particles generated after plasma irradiation (plasma resistance) and a small compression set at high temperature (heat resistance), preferred among these is silicon carbide.
  • Hydrophobic silica for example, can reduce the compression set but unfortunately increases the weight reduction percentage after NF 3 plasma irradiation, i.e., has insufficient plasma resistance.
  • silicon carbide without surface oxidation can reduce the weight reduction percentage and amount of particles generated after plasma irradiation but unfortunately increases the compression set at high temperature, i.e., has insufficient heat resistance.
  • the surfaces thereof are oxidized into SiO 2 .
  • a peak assigned to SiO 2 and a peak assigned to SiC are observed.
  • the peak assigned to SiO 2 and the peak assigned to SiC preferably give a ratio (SiO 2 :SiC) of 1:9 to 9:1, more preferably 3:7 to 6:4.
  • a peak ratio of less than 1:9 tends to cause insufficient surface oxidation and fails to achieve a sufficient effect of improvement.
  • a peak ratio of more than 9:1 tends to cause excessive surface oxidation and fail to achieve a sufficient effect of improvement.
  • the non-oxide ceramic is preferably powdered by a pulverization using a pulverizer such as a jet mill or by powder formation in which a nuclear is generated and grown from an atom or a molecule.
  • a pulverizer such as a jet mill
  • methods are sorted into a gas phase method, a liquid phase method, and a solid phase method, according to the state of the starting material. Any method may be employed as long as the resulting powder of the non-oxide ceramic has a sufficient purity.
  • silicon carbide preferably has a purity of 95% or higher in order to achieve excellent plasma resistance.
  • the non-oxide ceramic filler may be in any form, such as powder, particles, fibers, and whiskers.
  • the non-oxide ceramic filler is preferably in the form of particles in terms of processability and preferably has an average particle size of 10 um or smaller, more preferably 0.1 um or smaller.
  • the non-oxide ceramic filler having an average particle size of greater than 10 um may cause poor reinforcement and thus a greater amount of the non-oxide ceramic filler may need to be added to a compound, impairing the characteristics of a resulting molded article as a seal material.
  • the non-oxide ceramic filler has an average particle size of 0.1 um or smaller, preferably 0.01 to 0.1 um, in order to reduce generation of particles.
  • the lower limit of the average particle size is not limited.
  • the percentage of the non-oxide ceramic filler whose surfaces are oxidized to a depth of 2 nm or more is preferably, but not limited to, 10 to 100% by mass, more preferably 30 to 100% by mass, in 100% by mass of the non-oxide ceramic filler.
  • the non-oxide ceramic filler is present at any amount, preferably 1 to 40 parts by mass, more preferably 5 to 25 parts by mass, relative to 100 parts by mass of the crosslinkable elastomer.
  • a preferred amount of the non-oxide ceramic filler depends on the average particle size of the non-oxide ceramic filler.
  • the amount of the non-oxide ceramic filler having an average particle size of 0.01 to 0.1 um is more preferably 1 to 40 parts by mass, still more preferably 5 to 25 parts by mass, relative to 100 parts by mass of the crosslinkable elastomer.
  • the amount of the non-oxide ceramic filler having an average particle size of 0.1 to 10 um is more preferably 5 to 50 parts by mass, still more preferably 10 to 30 parts by mass.
  • the non-oxide ceramic filler may be surface-oxidized by any method, such as heat treatment in the air, acid treatment, ozone treatment, or oxygen plasma treatment.
  • the heat treatment may be performed under any conditions.
  • the temperature for the heat treatment is preferably 500°C to 1000°C, more preferably 700°C to 900°C.
  • a temperature lower than 500°C tends to cause less surface oxidation.
  • a temperature higher than 1000°C excessively tends to increase the surface oxidation rate to cause difficulty in controlling the thickness of the oxidized layer, resulting in excessive oxidation even inside the particles.
  • the duration of the heat treatment is preferably 0.1 to 24 hours, more preferably 0.2 to 4 hours.
  • Any acid may be used for the acid treatment, and examples thereof include sulfuric acid aqueous solution, hydrogen peroxide solution, nitric acid, a mixed acid of these.
  • the acid treatment may be performed under any conditions.
  • the temperature for the treatment is preferably 20°C to 100°C, and the duration of the treatment is preferably 0.1 to 24 hours, more preferably 0.2 to 4 hours.
  • the ozone treatment may be performed under any conditions, preferably at an ozone concentration of 100 to 300 g/N ⁇ m 3 , a discharge amount of 40 to 80%, a cell pressure of 0.1 to 0.3 MPa, an O 2 flow rate of 2 to 5 L/min, a N 2 flow rate of 3 to 10 cc/min, and a temperature of 100°C to 200°C.
  • the oxygen plasma treatment may be performed under any conditions, preferably at a power of 200 to 1000 W, an O 2 flow rate of 10 to 30 sccm, a pressure of 1 to 5 Pa, an irradiation temperature of 20°C to 200°C, and an irradiation time of 0.1 to 1 hr.
  • the crosslinkable elastomer used may be a fluorine elastomer or a silicone elastomer. From the viewpoints of the heat resistance and the resistance to all types of plasma, a fluorine-containing elastomer is preferred.
  • the fluorine-containing elastomer used in the invention may be any of those conventionally used for sealing materials, particularly sealing materials for semiconductor manufacturing devices.
  • fluorine-containing elastomer examples include a fluoroelastomer (a), a thermoplastic fluoroelastomer (b) and a rubber composition containing these fluoroelastomers.
  • fluoroelastomer (a) examples include non-perfluoro fluoroelastomer (a-1) and perfluoro fluoroelastomer (a-2).
  • thermoplastic fluoroelastomer (b) examples include a fluorine-containing multi-segmented polymer (b-1) containing an elastomeric fluorine-containing polymer chain segment and a non-elastomeric fluorine-containing polymer chain segment with at least 90 mol% of the structural units of both the elastomeric fluorine-containing polymer chain segment and the non-elastomeric fluorine-containing polymer chain segment being perhalo olefins; a fluorine-containing multi-segmented polymer (b-2) containing an elastomeric fluorine-containing polymer chain segment and a non-elastomeric fluorine-containing polymer chain segment with at least 90 mol% of the structural units of the elastomeric fluorine-containing polymer chain segment being perhalo olefins and with the non-elastomeric fluorine-containing polymer chain segment containing less than 90 mol% of perhalo olefins as structural
  • non-perfluoro fluoroelastomer (a-1) examples include a vinylidene fluoride (VdF) fluoroelastomer, a tetrafluoroethylene (TFE)/propylene fluoroelastomer, a tetrafluoroethylene (TFE)/propylene/vinylidene fluoride (VdF) fluoroelastomer, an ethylene/hexafluoroethylene (HFP) fluoroelastomer, an ethylene/hexafluoroethylene (HFP)/vinylidene fluoride (VdF) fluoroelastomer, an ethylene/hexafluoropropylene (HFP)/tetrafluoroethylene (TFE) fluoroelastomer, a fluorosilicone fluoroelastomer, and a fluorophosphazene fluoroelastomer. These may be used alone or may be used in any combination as long
  • the vinylidene fluoride fluoroelastomer refers to a fluorine-containing elastic copolymer containing 45 to 85 mol% of vinylidene fluoride and 55 to 15 mol% of at least one different monomer copolymerizable with vinylidene fluoride, preferably a fluorine-containing elastic copolymer containing 50 to 80 mol% of vinylidene fluoride and 50 to 20 mol% of at least one different monomer copolymerizable with vinylidene fluoride.
  • Examples of the at least one different monomer copolymerizable with vinylidene fluoride include fluorine-containing monomers such as tetrafluoroethylene (TFE), chlorotrifluoroethylene (CTFE), trifluoroethylene, hexafluoropropylene (HFP), trifluoropropylene, tetrafluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutene, perfluoro(alkyl vinyl ether) (PAVE), and vinyl fluoride and nonfluorine-containing monomers such as ethylene, propylene, and alkyl vinyl ether. These may be used alone or may be used in any combination. Preferred among these are tetrafluoroethylene, hexafluoropropylene, and perfluoro(alkyl vinyl ether).
  • rubber examples include VdF-HFP rubber, VdF-HFP-TFE rubber, VdF-CTFE rubber, and VdF-CTFE-TFE rubber.
  • the vinylidene fluoride fluoroelastomer can be obtained by a usual method.
  • the tetrafluoroethylene/propylene fluoroelastomer refers to a fluorine-containing elastic copolymer containing 45 to 70 mol% of tetrafluoroethylene, 55 to 30 mol% of propylene, and 0 to 5 mol% of a monomer that gives a crosslinking site.
  • Examples of the monomer that gives a crosslinking site include iodine-containing monomers such as perfluoro(6,6-dihydro-6-iodo-3-oxa-1-hexene) and perfluoro(5-iodo-3-oxa-1-pentene) described in JP H05-63482 B and JP H07-316234 A , bromine-containing monomers described in JP H04-505341 A , monomers containing a nitrile group, monomers containing a carboxyl group, and monomers containing an alkoxycarbonyl group described in JP H04-505345 A and JP H05-500070 A .
  • iodine-containing monomers such as perfluoro(6,6-dihydro-6-iodo-3-oxa-1-hexene) and perfluoro(5-iodo-3-oxa-1-pentene) described in JP H05-63482 B and JP
  • the tetrafluoroethylene/propylene fluoroelastomer can also be obtained by a usual method.
  • non-perfluoro fluoroelastomers (a-1) can be prepared by a usual method.
  • Examples of commercially available products of the non-perfluoro fluoroelastomer (a-1) include DAI-EL G-800 series and DAI-EL G-900 series available from Daikin Industries, Ltd.
  • perfluoro fluororubber (a-2) is a copolymer containing tetrafluoroethylene and perfluoro(alkyl vinyl ether), such as a fluorine-containing elastic copolymer containing tetrafluoroethylene/perfluoro(alkyl vinyl ether)/a monomer that gives a crosslinking site.
  • the composition thereof is preferably (45 to 90)/(10 to 50)/(0 to 5) (mol%), more preferably (45 to 80)/(20 to 50)/(0 to 5), further preferably (53 to 70)/(30 to 45)/(0 to 2).
  • perfluoro(alkyl vinyl ether) examples include perfluoro(methyl vinyl ether) and perfluoro(propyl vinyl ether). These may be used alone or may be used in any combination as long as the effects of the invention are not impaired.
  • CY 1 2 CY 2 R f 2 X 3 (wherein Y 1 and Y 2 are each H, F, or CH 3 ; R f 2 is a linear or branched fluorine-containing alkylene group whose hydrogen atoms are partially or completely substituted with fluorine atoms and which optionally contains at least one oxygen atom as an ether bond and optionally contains an aromatic ring; and X 3 is an iodine group, a bromine group, a nitrile group, a carboxyl group, an alkoxycarbonyl group, an azide group, or an alkyne group).
  • the iodine and nitrile groups can function as crosslinking sites.
  • the perfluoro fluoroelastomer (a-2) can be prepared by a usual method.
  • perfluoro fluoroelastomer (a-2) examples include fluoroelastomers described in WO97/24381 , JP S61-57324 B , JP H04-81608 B , and JP H05-13961 B .
  • the fluorine-containing multi-segmented polymer (b-1) which is the thermoplastic fluoroelastomer (b) is described below.
  • the fluorine-containing multi-segmented polymer (b-1) contains an elastomeric fluorine-containing polymer chain segment and a non-elastomeric fluorine-containing polymer chain segment. At least 90 mol% of the structural units of both the elastomeric fluorine-containing polymer chain segment and the non-elastomeric fluorine-containing polymer chain segment are perhalo olefins.
  • the elastomeric fluorine-containing polymer chain segment is described.
  • the elastomeric fluorine-containing polymer chain segment imparts flexibility to the polymer and has a glass transition temperature of at most 25°C, preferably at most 0°C.
  • the perhalo olefins that constitute at least 90 mol% of the structural units thereof include tetrafluoroethylene, chlorotrifluoroethylene, hexafluoropropylene, and fluorovinylether represented by the following formula (3):
  • CF 2 CFO(CF 2 CFYO) p -(CF 2 CF 2 CF 2 O) q -Rf (wherein Y is F or CF 3 ; Rf is a C1-C5 perfluoroalkyl group; p is an integer of 0 to 5; and q is an integer of 0 to 5).
  • Examples of the structural units other than the perhalo olefins that constitute the elastomeric fluorine-containing polymer chain segment include fluorine-containing monomers such as vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, trifluoropropylene, tetrafluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutene, and vinyl fluoride and nonfluorine-containing monomers such as ethylene, propylene, and alkyl vinyl ether.
  • fluorine-containing monomers such as vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, trifluoropropylene, tetrafluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutene, and vinyl fluoride and nonfluorine-containing monomers such as ethylene, propylene, and
  • a preferred example of the elastomeric fluorine-containing polymer chain segment is an elastic polymer chain containing tetrafluoroethylene/perfluoro(alkyl vinyl ether)/a monomer that gives a crosslinking site.
  • the composition thereof is preferably (50 to 85)/(50 to 15)/(0 to 5) (mol%).
  • CY 1 2 CY 2 R f 2 X 3 (wherein Y 1 and Y 2 are each H, F, or CH 3 ; R f 2 is a linear or branched fluorine-containing alkylene group whose hydrogen atoms are partially or completely substituted with fluorine atoms and which optionally contains at least one oxygen atom as an ether bond and optionally contains an aromatic ring; and X 3 is an iodine group, a bromine group, a nitrile group, a carboxyl group, an alkoxycarbonyl group, an azide group, or an alkyne group).
  • the iodine, bromine, nitrile, carboxyl, and alkoxycarbonyl groups can function as crosslinking sites.
  • the non-elastomeric fluorine-containing polymer chain segment is described.
  • Examples of the structural units other than the perhalo olefins that constitute the non-elastomeric fluorine-containing polymer chain segment include fluorine-containing monomers such as vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, trifluoropropylene, tetrafluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutene, and vinyl fluoride and nonfluorine-containing monomers such as ethylene, propylene, and alkyl vinyl ether.
  • fluorine-containing monomers such as vinylidene fluoride, trifluoroethylene, tetrafluoroethylene, trifluoropropylene, tetrafluoropropylene, pentafluoropropylene, trifluorobutene, tetrafluoroisobutene, and vinyl fluoride and nonfluorine-containing monomers such as ethylene, propylene,
  • the crystal melting point of the non-elastomeric fluorine-containing polymer chain segment is at least 150°C, preferably 200°C to 360°C.
  • the fluorine-containing multi-segmented polymer (b-1) is a fluorine-containing multi-segmented polymer in which an elastomeric fluorine-containing polymer chain segment and a non-elastomeric fluorine-containing polymer chain segment are bonded by blocking or grafting in each molecule.
  • the fluorine-containing multi-segmented polymer (b-1) may be produced by a variety of known processes in which an elastomeric segment and a non-elastomeric segment are connected by blocking or grafting to form a fluorine-containing multi-segmented polymer.
  • the process for preparing a block-type fluorine-containing multi-segmented polymer described in JP S58-04728 B and the process for preparing a graft-type fluorine-containing multi-segmented polymer described in JP S62-34324 A are preferably employed.
  • a block-type fluorine-containing multi-segmented polymer synthesized by the iodine transfer polymerization method described in JP S58-04728 B and KOBUNSHI RONBUNSHU Japanese Journal of Polymer Science and Technology (Vol. 49, No. 10, 1992 ).
  • a mere mixture of an elastomeric fluorine-containing polymer and a non-elastomeric fluorine-containing polymer may usually have insufficient mechanical properties (particularly at high temperatures) and reduced abrasion resistance, flexibility, and durability, although the effects differ according to the type, mixing properties, and compatibility of each polymer mixed.
  • a multi-segmented polymer prepared by bonding an elastomeric segment and a non-elastomeric segment by blocking or grafting can have improved heat resistance and mechanical properties (particularly at high temperatures) in comparison to the mere mixture of an elastomeric fluorine-containing polymer and a non-elastomeric fluorine-containing polymer.
  • the elastomeric segment can be prepared by the iodine transfer polymerization method, which is known as a process for preparing a fluoroelastomer ( JP S58-04728 B , JP S62-12734 A ).
  • An example is a method of emulsion polymerizing a perhalo olefin and, if necessary, a monomer that gives a crosslinking site using a radical initiator in an aqueous medium with an iodine compound, preferably a diiodine compound, in a substantially oxygen-free atmosphere, while stirring the component under pressure.
  • diiodine compound used examples include 1,3-diiodoperfluoropropane, 1,4-diiodoperfluorobutane, 1,3-diiodo-2-chloroperfluoropropane, 1,5-diiodo-2,4-dichloroperfluoropentane, 1,6-diiodoperfluorohexane, 1,8-diiodoperfluorooctane, 1,12-diiodoperfluorododecane, 1,16-diiodoperfluorohexadecane, diiodomethane, and 1,2-diiodoethane.
  • the amount of the diiodine compound is 0.01 to 1% by mass relative to the total mass of the elastomeric segment.
  • the elastomeric segment obtained in this way has a perhalo-type terminal and has an iodine atom that is the initiation point of block copolymerization of the non-elastomeric segment.
  • the radical polymerization initiator used for preparing the elastomeric segment in the invention may be an initiator conventionally used for production of a fluorine elastomer by polymerization.
  • an initiator include organic and inorganic peroxides and azo compounds.
  • typical initiators include persulfates, carbonate peroxides, and ester peroxides, and a preferred initiator is ammonium persulfate (APS).
  • APS may be used alone or may be used in combination with a reducing agent such as a sulfite or a sulfurous acid salt.
  • the elastomeric segment obtained in this way preferably has a number average molecular weight of 5,000 to 750,000, particularly 20,000 to 400,000, from the viewpoint of imparting flexibility, elasticity, and mechanical properties to the entire fluorine-containing multi-segmented polymer.
  • block copolymerization of the non-elastomeric segment can be performed subsequent to the emulsion polymerization of the elastomeric segment by changing the monomer into those for the non-elastomeric segment.
  • the number average molecular weight of the non-elastomeric segment can be adjusted within a wide range of 1,000 to 1,200,000, preferably 3,000 to 600,000.
  • the fluorine-containing multi-segmented polymer (b-1) obtained in this way is composed mainly of polymer molecules in which non-elastomeric segments are bonded to both sides of the elastomeric segment and polymer molecules in which non-elastomeric segments are bonded to one side of the elastomeric segment.
  • the amount of polymer molecules consisting of elastomeric segments and containing no elastomeric segments bonded thereto is at most 20% by mass, preferably at most 10% by mass, relative to the total amount of the segments and the polymer molecules in the fluorine-containing multi-segmented polymer.
  • the fluorine-containing multi-segmented polymer (b-2) is described below.
  • the fluorine-containing multi-segmented polymer (b-2) contains an elastomeric fluorine-containing polymer chain segment and a non-elastomeric fluorine-containing polymer chain segment. At least 90 mol% of the structural units of the elastomeric fluorine-containing polymer chain segment are perhalo olefins and the non-elastomeric fluorine-containing polymer chain segment contains less than 90 mol% of perhalo olefins as structural units.
  • the elastomeric fluorine-containing polymer chain segment thereof is the same as that given for the fluorine-containing multi-segmented polymer (b-1).
  • the non-elastomeric fluorine-containing polymer chain segment is a polymer chain having a crystal melting point of at least 150°C, preferably 200°C to 360°C.
  • monomers that are copolymerizable with these monomers such as ethylene, propylene, vinyl chloride, vinyl ether, vinyl carboxylate, and acrylic acid may be used as copolymerization components.
  • the fluorine-containing multi-segmented polymer (b-2) can be prepared in the same manner as the fluorine-containing multi-segmented polymer (b-1).
  • the fluorine-containing multi-segmented polymer (b-3) is described below.
  • the fluorine-containing multi-segmented polymer (b-3) contains an elastomeric fluorine-containing polymer chain segment and a non-elastomeric fluorine-containing polymer chain segment.
  • the elastomeric fluorine-containing polymer chain segment contains less than 90 mol% of perhalo olefins as structural units and at least 90 mol% of the structural units of the non-elastomeric fluorine-containing polymer chain segment are perhalo olefins or the non-elastomeric fluorine-containing polymer chain segment contains less than 90 mol% of perhalo olefins as structural units.
  • the elastomeric fluorine-containing polymer chain segment of the fluorine-containing multi-segmented polymer (b-3) is a polymer chain having a glass transition point of at most 25°C, preferably at most 0°C.
  • the elastomeric fluorine-containing polymer chain segment contains less than 90 mol% of perhalo olefins as structural units.
  • Examples of the structural units other than the perhalo olefins are the same as those given for the vinylidene fluoride fluoroelastomer, which is a non-perfluoro fluoroelastomer (a-1).
  • the non-elastomeric fluorine-containing polymer chain segment of the fluorine-containing multi-segmented polymer (b-3) is the same as the non-elastomeric fluorine-containing polymer chain segment in the fluorine-containing multi-segmented polymer (b-1) or (b-2), preferably the same as the non-elastomeric fluorine-containing polymer chain segment in (b-2).
  • the fluorine-containing multi-segmented polymer (b-3) contains 40 to 95% by mass of the elastomeric fluorine-containing polymer chain segment and 5 to 60% by mass of the non-elastomeric fluorine-containing polymer chain segment.
  • the fluorine-containing multi-segmented polymer (b-3) can be prepared in the same manner as the fluorine-containing multi-segmented polymers (b-1) and (b-2).
  • fluorine-containing multi-segmented polymer (b-3) examples include DAI-EL Thermo T-530, T-550, and T-630 available from Daikin Industries, Ltd. and CEFRAL SOFT available from Central Glass Co., Ltd.
  • composition containing the fluoroelastomer (a) and the thermoplastic fluoroelastomer described above may be used.
  • a first fluoroelastomer composition containing the non-perfluoro fluoroelastomer (a-1) and the fluorine-containing multi-segmented polymer (b-1) can be obtained by mixing the non-perfluoro fluoroelastomer (a-1) and the fluorine-containing multi-segmented polymer (b-1) at any ratio in the form of dispersion or by dry blending these at any ratio with an open roll.
  • additives such as an internal mold release agent may be added as appropriate as long as the effects of the invention are not impaired.
  • a second fluoroelastomer composition containing the non-perfluoro fluoroelastomer (a-1) and the fluorine-containing multi-segmented polymer (b-2) can be obtained in the same manner as the first fluoroelastomer composition.
  • the above additive may be added as appropriate as long as the effects of the invention are not impaired and a cross-linking agent may be added in accordance with the type of the crosslinking method described below.
  • a third fluoroelastomer composition containing the perfluoro fluoroelastomer (a-2) and the fluorine-containing multi-segmented polymer (b-3) can be obtained in the same manner as the first fluoroelastomer composition.
  • the above additive may be added as appropriate as long as the effects of the invention are not impaired and a cross-linking agent may be added in accordance with the type of the crosslinking method described below.
  • a fourth fluoroelastomer composition containing the perfluoro fluoroelastomer (a-2) and the fluorine-containing multi-segmented polymer (b-1) can be obtained in the same manner as the first fluoroelastomer composition.
  • Both the perfluoro fluoroelastomer (a-2) and the fluorine-containing multi-segmented polymer (b-1) are poor in crosslinking efficiency by radiation and substantially cannot be crosslinked by radiation. Therefore, a crosslinking site which enables peroxide crosslinking, for example, needs to be introduced into at least one of the rubbers for crosslinking.
  • a preferred example of the fluoroelastomer with a crosslinking site introduced therein is a fluoroelastomer with iodine or bromine introduced into a polymer terminal.
  • This fluoroelastomer is obtained by introducing a compound represented by the following formula (9): RI x Br y (wherein R is a C1-C16 saturated or unsaturated fluorohydrocarbon or chlorofluorohydrocarbon group or a C1-C3 hydrocarbon group; and x and y are each an integer of 0 to 2 and 1 ⁇ x + y ⁇ 2) in preparation by polymerization.
  • the iodine or bromine that is introduced in this way functions as a crosslinking site.
  • RI x Br y examples include 1,3-diiodoperfluoropropane, 1,3-diiodo-2-chloroperfluoropropane, 1,4-diiodoperfluorobutane, 1,5-diiodo-2,4-dichloroperfluoropentane, 1,6-diiodoperfluorohexane, 1,8-diiodoperfluorooctane, 1,12-diiodoperfluorododecane, 1,16-diiodoperfluorohexadecane, diiodomethane,
  • the amount of the compound represented by the following formula (9): RI x Br y (wherein R is a C1-C16 saturated or unsaturated fluorohydrocarbon or chlorofluorohydrocarbon group or a C1-C3 hydrocarbon group; and x and y are each an integer of 0 to 2 and 1 ⁇ x + y ⁇ 2) is 0.0001 to 5% by mass, preferably 0.01 to 1% by mass of the total mass of the fluoroelastomer to be obtained.
  • Another method for introducing a crosslinking site is a method of copolymerizing a small amount of a monomer that gives a crosslinking site.
  • Preferred examples of such a monomer include iodine-containing monomers such as perfluoro(6,6-dihydro-6-iodo-3-oxa-1-hexene) and perfluoro(5-iodo-3-oxa-1-pentene) described in JP H05-63482 B and JP H07-316234 A , bromine-containing monomers described in JP H04-505341 A , a monomer containing a nitrile group, a monomer containing a carboxyl group, and a monomer containing an alkoxycarbonyl group described in JP H04-505345 A and JP H05-500070 A .
  • iodine-containing monomers such as perfluoro(6,6-dihydro-6-iodo-3-oxa-1-hexene) and perfluoro(5-iodo-3-oxa-1-pentene) described in JP H05-63482 B and
  • a fifth fluoroelastomer composition containing the perfluoro fluoroelastomer (a-2) and the fluorine-containing multi-segmented polymer (b-2) can be obtained in the same manner as the first fluoroelastomer composition.
  • the above additive may be added as appropriate as long as the effects of the invention are not impaired and a cross-linking agent may be added in accordance with the type of the crosslinking method described below.
  • the monomer mixed gas used in the invention is explosive, as described by G. H. Kalb et al., in Advances in Chemistry Series, 129, 13 (1973 ), and the polymerization device needs to be designed so that sparks, which become an ignition source, are not generated.
  • the polymerization pressure is preferably kept as low as possible.
  • the polymerization pressure can be changed in a wide range and is usually within the range of 0.5 to 5 MPa.
  • the polymerization pressure is preferably at least 0.8 MPa.
  • Some of the polymerization products obtained in this way under certain polymerization conditions may contain no free carboxyl groups. Still, the following acid treatment enables conversion into free carboxyl groups.
  • silicone elastomer used in the invention examples include silicone rubber and fluorosilicone rubber.
  • Preferred among the crosslinkable elastomers obtained in this way as the fluorine-containing elastomer used in the invention is a copolymer containing tetrafluoroethylene/perfluoro(alkyl vinyl ether)/a monomer having a crosslinkable functional group, from the viewpoints of heat resistance and chemical resistance.
  • perfluoro(alkyl vinyl ether) examples include perfluoro(methyl vinyl ether) (PMVE), perfluoro(ethyl vinyl ether) (PEVE), and perfluoro(propyl vinyl ether) (PPVE). Preferred among these is PMVE because it has excellent cold resistance.
  • the monomer for introducing a crosslinking site is preferably an iodine-containing monomer, a monomer containing a nitrile group, a monomer containing a carboxyl group, or a monomer containing an alkoxycarbonyl group.
  • a monomer containing a nitrile group is more preferred from the viewpoints of the crosslinking reactivity and the heat resistance of the crosslinking structure formed by the crosslinking reaction.
  • An example of the method for introducing a carboxyl group, an alkoxycarbonyl group, an iodine atom, a bromine atom, or a sulfonic acid group into a polymer terminal group of the crosslinkable elastomer is the acid treatment described below.
  • the above crosslinkable elastomer can be prepared by polymerization methods such as emulsion polymerization, suspension polymerization, and solution polymerization.
  • the emulsifier used for emulsion polymerization may be selected from a wide range.
  • the amount of the emulsifier is preferably about 0.05 to 2% by mass, more preferably 0.2 to 1.5% by mass of the amount of water that is added.
  • the polymerization initiator used for production of the crosslinkable elastomer by polymerization is preferably an initiator capable of introducing a carboxyl group or a group capable of producing a carboxyl group (e.g., acid fluoride, acid chloride, CF 2 OH, all of which produce a carboxyl group in the presence of water) into an elastomer terminal.
  • a carboxyl group e.g., acid fluoride, acid chloride, CF 2 OH, all of which produce a carboxyl group in the presence of water
  • Specific examples include ammonium persulfate (APS) and potassium persulfate (KPS).
  • a chain transfer agent that is usually used to adjust the molecular weight may be used, but is preferably used as little as possible because it reduces the proportion of the group capable of producing a carboxyl or alkoxycarbonyl group that is introduced a terminal. However, this does not apply when the chain transfer agent is capable of introducing the above group into an elastomer terminal.
  • the molecular weight can be adjusted by performing polymerization under low pressure, for example less than 2 MPa ⁇ G, more preferably at most 1 MPa ⁇ G. Other polymerization conditions are not limited.
  • the pH of the polymerization system is preferably set to at most 3, i.e., a strong acidic value.
  • groups such as a metallic salt and ammonium salt of a carboxylic acid that are present in the polymerization product are preferably converted into carboxyl groups by acid treatment on the polymerization product.
  • Suitable methods for acid treatment include a method of cleaning with hydrochloric acid, sulfuric acid, or nitric acid and a method of adjusting the pH of the system of a mixture after the polymerization reaction to at most 3 with these acids.
  • this acid treatment is preferably applied as an agglomeration technique for isolating the polymerization product from the polymerization reaction mixture by agglomeration.
  • the polymerization mixture may be subjected to acid treatment and then the polymer product may be isolated by lyophilization, for example.
  • a method of agglomeration by ultrasonic waves or mechanical power may be employed.
  • a carboxyl group may be introduced by oxidizing a crosslinkable elastomer containing iodine or bromine with fuming nitric acid.
  • curing agent used in the invention examples include peroxide crosslinking curing agents, polyol crosslinking curing agents, polyamine crosslinking curing agents, triazine crosslinking curing agents, oxazole crosslinking curing agents, imidazole crosslinking curing agents, thiazole crosslinking curing agents, and radiation crosslinking curing agents.
  • the curing agent used in peroxide crosslinking is an organic peroxide that can easily produce a peroxy radical in the presence of heat or a redox system.
  • organic peroxide that can easily produce a peroxy radical in the presence of heat or a redox system.
  • Specific examples thereof include 1,1-bis(t-butylperoxy)-3,5,5-trimethylcyclohexane, 2,5-dimethylhexane-2,5-dihydroperoxide, di-t-butyl peroxide (Perbutyl D), t-butylcumyl peroxide (Perbutyl C), dicumyl peroxide (Percumyl D, Percumyl D-40, Percumyl D-40MB(T)), ⁇ , ⁇ -bis(t-butylperoxy)-p-diisopropylbenzene, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane (Perhexa 25B, Per
  • dialkyl curing agents Preferred among these are dialkyl curing agents, and particularly preferred is 2,5-dimethyl-2,5-di(t-butylperoxy)hexane.
  • the type and amount of the organic peroxide are selected in consideration of the amount of active -O-O- and the decomposition temperature.
  • the curing aid to be used in this case is a compound having reactivity with a peroxy radical and a polymer radical.
  • triallyl cyanurate triallyl isocyanurate (TAIC), triacrylformal, triallyl trimellitate, N,N'-n-phenylene bismaleimide, dipropargyl terephthalate, diallyl phthalate, tetraallyl terephthalate amide, triallyl phosphate, bismaleimide, fluorinated triallyl isocyanurate (1,3,5-tris(2,3,3-trifluoro-2-propenyl)-1,3,5-triazine-2,4,6-trione), tris(diallylamine)-S-triazine, triallyl phosphite, N,N-diallyl acrylamide, 1,6-divinyl dodecafluorohexane, and a compound represented by the following formula (I): (wherein R 1 , R 2 , R 3 , R 4 , R 5 , and R 6 are the same as or different from each other and are each H,
  • Examples of the compound represented by the formula (I) include:
  • R VI1 to R VI3 are each independently a hydrogen atom, a fluorine atom, an alkyl group, a fluorinated alkyl group, or a substituted or non-substituted aryl group, at least one selected from R VI1 to R VI3 is a fluorine atom or a group containing a fluorine atom; m is an integer of 1 to 5; when m is 2 or greater, the m R VI1 s to R VI3 s are the same as or different from each other; and hydrogen atom(s) in the benzene ring may be substituted).
  • m 1, the compound preferably contains two or more of the structures.
  • the hetero atom-containing group is a group containing a hetero atom other than a carbon atom.
  • the hetero atom include an oxygen atom, a nitrogen atom, and a sulfur atom.
  • the hetero atom-containing group include -O-, -S-, -SO 2 -, and -CO-.
  • R VI1 to R VI3 are as defined above; p is an integer of 0 to 2; and n is an integer of 2 to 6).
  • curing agent used in polyol crosslinking examples include polyhydric alcohol compounds such as bisphenol A and bisphenol AF.
  • curing agent used in polyamine crosslinking examples include polyamine compounds such as hexamethylenediamine carbamate, N,N'-dicinnamylidene-1,6-hexanediamine, and 4,4'-bis(aminocyclohexyl)methanecarbamate.
  • Examples of the curing agent used in triazine crosslinking include organic tin compounds such as tetraphenyl tin and triphenyl tin.
  • organic tin compounds such as tetraphenyl tin and triphenyl tin.
  • a non-oxide filler such as silicon nitride may also be used.
  • Examples of the curing agent used in oxazole crosslinking, imidazole crosslinking, and thiazole crosslinking include a bisdiaminophenyl curing agent, a bisaminophenol curing agent, and a bisaminothiophenol curing agent, each represented by the following formula (10) : (wherein R 1 is -SO 2 -, -O-, -CO-, a C1-C6 alkylene group, a C1-C10 perfluoroalkylene group, or a single bond; and one selected from R 2 and R 3 is -NH 2 and the other is -NH 2 , -OH or -SH, preferably both R 2 and R 3 are -NH 2 ), a bisamidrazone curing agent represented by the following formula (11): or a bisamidoxime curing agent represented by the following formula (12) or (13): (wherein R f is a C1-C10 perfluoroalkylene group), (wherein n
  • bisaminophenol curing agent bisaminothiophenol curing agent, and bisdiaminophenyl curing agent have been conventionally used in a crosslinking system in which the crosslinking site is a nitrile group, and also react with a carboxyl group and an alkoxycarbonyl group and form an oxazole ring, thiazole ring, and an imidazole ring, respectively, to give a crosslinked article.
  • a bisdiaminophenyl curing agent having at least two bisamino crosslinkable functional groups represented by the following formula (14): (wherein R 5 is a fluorine atom or a monovalent organic group).
  • R 5 is a fluorine atom or a monovalent organic group.
  • a functional group that can be reacted with the crosslinkable functional groups include a nitrile group, a carboxyl group, and an alkoxycarbonyl group, and an imidazole ring is formed by the reaction.
  • a still more preferred curing agent is a compound represented by the following formula (15):
  • the substitutent R 6 in each crosslinkable reactive group is a monovalent organic group other than hydrogen or a fluorine atom, and a substitutent that forms an N-R 6 bond having higher oxidization resistance than an N-H bond is particularly preferred.
  • a substitutent that forms an N-R 6 bond having higher oxidization resistance than an N-H bond refers to a substitutent that forms an N-R 6 bond that is present in a compound that is less likely to be oxidized than a compound having an N-H bond when an imidazole ring is formed.
  • R 6 examples include, but are not limited to, an aliphatic hydrocarbon group that may be substituted, a phenyl group that may be substituted, or a benzyl group.
  • R 6 is a lower alkyl group having 1 to 10, preferably 1 to 6 carbon atoms, such as -CH 3 , -C 2 H 5 , and -C 3 H 7 ; a fluorine-containing lower alkyl group having 1 to 10, preferably 1 to 6 carbon atoms, such as -CF 3 , -C 2 F 5 , -CH 2 F, -CH 2 CF 3 , and -CH 2 C 2 F 5 ; a phenyl group; a benzyl group; a phenyl group or a benzyl group wherein 1 to 5 hydrogen atoms are each substituted with a fluorine atom, such as - C 6 F 5 and -CH 2 C 6 F 5 ; and a phenyl or benzyl group wherein 1 to 5 hydrogen atoms are each substituted with -CF 3 , such as - C 6 H 5 -n (CF 3 ) n and -CH 2 C
  • Preferred among these are a phenyl group and -CH 3 from the viewpoints of particularly excellent heat resistance, favorable crosslinking reactivity, and relatively easy synthesis.
  • R 7 is -SO 2 -, -O-, -CO-, an alkylene group that may be substituted, or a single bond.
  • alkylene group that may be substituted for R 7 include, but are not limited to, a C1-C6 nonsubstituted alkylene group and a C1-C10 perfluoroalkylene group.
  • perfluoroalkylene group is
  • R 7 are known as examples of bisdiaminophenyl compounds from JP H02-59177 B and JP H08-120146 A .
  • R 7 may be bonded to any position of both the right and left benzene rings. From the viewpoint of easy synthesis and easy progress of a crosslinking reaction, either an -NH 2 group or an -NHR 7 is preferably bonded at the para position.
  • a particularly preferred example of the curing agent is a compound represented by the following formula (16): (wherein R 8 s are the same or different from each other and are each a C1-C10 alkyl group, a C1-C10 alkyl group containing a fluorine atom, a phenyl group, a benzyl group, or a phenyl or benzyl group wherein 1 to 5 hydrogen atoms are each substituted with a fluorine atom or -CF 3 ).
  • Examples thereof include, but are not limited to, 2,2-bis-[3-amino-4-(N-methylamino)phenyl]hexafluoropropane, 2,2-bis-[3-amino-4-(N-ethylamino)phenyl]hexafluoropropane, 2,2-bis-[3-amino-4-(N-propylamino)phenyl]hexafluoropropane, 2,2-bis-[3-amino-4-(N-phenylamino)phenyl]hexafluoropropane, 2,2-bis-[3-amino-4-(N-perfluorophenylamino)phenyl]hexafluoropropane, 2,2-bis-[3-amino-4-(N-benzylamino)phenyl]hexafluoropropane, 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane (generic name
  • the curing agents described above are excellent in mechanical strength, heat resistance, and chemical resistance and give an excellent crosslinked article having good balance in heat resistance and chemical resistance.
  • the amount of the curing agent for the crosslinkable elastomer is preferably 0.05 to 10 parts by mass, more preferably 1 to 5 parts by mass, relative to 100 parts by mass of the crosslinkable elastomer. Less than 0.05 part by mass of the curing agent tends to cause insufficient crosslinking of the crosslinkable elastomer. More than 10 parts by mass of the curing agent tends to cause poor physical properties of the crosslinked article.
  • the crosslinkable elastomer composition of the invention may further contain an organic base compound.
  • the crosslinkable elastomer composition of the invention and the crosslinkable elastomer preferably contain a material produced under a condition substantially free from metal compounds.
  • the crosslinkable elastomer composition preferably has a metal content of 100 ppm or less, more preferably 50 ppm or less, still more preferably 10 ppm or less.
  • a crosslinkable elastomer composition having a quite small metal content is preferred because such a composition can provide a molded article usable in semiconductor manufacturing processes and pharmaceutical processes where contamination by metal components should be prevented.
  • the metal content can be measured by frame-less atomic adsorption analysis or high frequency inductively coupled plasma atomic emission spectroscopy.
  • the metal content in the invention refers to the total metal content of Fe, Cr, Ni, Cu, Al, Na, Mg, Ca, Zn, Ba, and K.
  • the total of the amount of these metals and the amount of the other metals may fall within the above range.
  • the crosslinkable elastomer composition of the invention can be prepared by mixing each of the above components using a usual elastomer processing machine such as an open roll, a Banbury mixer, or a kneader.
  • the composition can also be prepared by a method using an internal mixer and a method of co-coagulating the elastomer from an emulsion mixture.
  • the method for obtaining a pre-molded article from the above composition can be a usual method and can be a known method such as a method of heat-compressing the composition in a mold, a method of injecting the composition into a heated mold, or a method of extruding the composition with an extruder. Since extruded products such as a hose and an electric wire can maintain its shape after extrusion, the pre-molded article extruded without a cross-linking agent can be used as it is. A pre-molded article crosslinked by heating with steam using a cross-linking agent may also be used.
  • a molded article such as an O-ring
  • use of a pre-molded article that is crosslinked in advance using a cross-linking agent allows the article to maintain the shape.
  • the crosslinking can be performed under usual crosslinking conditions of a crosslinkable elastomer.
  • a crosslinked article can be obtained by press-crosslinking of maintaining the elastomer in a mold under pressure at 120°C to 200°C for 1 to 60 minutes and then oven-crosslinking of holding the elastomer in an oven at 120°C to 250°C for 0 to 48 hours.
  • the crosslinking can be performed under usual crosslinking conditions of a crosslinkable elastomer.
  • a crosslinked article can be obtained by press-crosslinking of placing the elastomer in a mold under pressure at 120°C to 250°C for 1 to 60 minutes and then oven-crosslinking of holding the elastomer in an oven at 120°C to 320°C for 0 to 48 hours.
  • a cross-linking agent such as bis(aminophenol)AF may be added to the composition for a known method for crosslinking a crosslinkable elastomer, such as polyamine cross-linking, polyol cross-linking, or peroxide cross-linking, for combined crosslinking.
  • Imidazole crosslinking in which a carboxyl group is crosslinked with a bisdiaminophenyl cross-linking agent is the most suitable for a carboxyl-containing polymer that has a carboxyl group in an area other than the terminals and gives a crosslinked article having favorable physical properties at a relatively low crosslinking temperature (e.g., 150°C to 230°C, preferably 170°C to 200°C).
  • the fluoroelastomer molded article of the invention has a weight reduction percentage of 2.5% by mass or less and an amount of particles generated of 0.05% by mass or less after O 2 plasma irradiation under the following conditions, a weight reduction percentage of 1.8% by mass or less and an amount of particles generated of 0.05% by mass or less after NF 3 plasma irradiation under the following conditions, and a compression set of 50% or less after aging at 300°C for 70 hours, the conditions being as follows.
  • Plasma irradiation device ICP high-density plasma device (MODEL RIE-101iPH available from Samco Inc.) Irradiation conditions
  • Plasma irradiation device ICP high-density plasma device (MODEL RIE-101iPH available from Samco Inc.) Irradiation conditions
  • Such a fluoroelastomer molded article of the invention can be produced from the aforementioned crosslinkable elastomer composition of the invention.
  • the weight reduction percentage after O 2 plasma irradiation is 2.5% by mass or less, preferably 1.5% by mass or less.
  • the weight reduction percentage has no particular lower limit because it is preferably as small as possible.
  • the amount of particles generated after O 2 plasma irradiation is 0.05% by mass or less, preferably 0.03% by mass or less.
  • the amount of particles generated has no particular lower limit because it is preferably as small as possible.
  • a weight reduction percentage of 2.5% by mass or less enables production of a seal material with better resistance to O 2 plasma, improving the long-term durability.
  • An amount of particles generated of 0.05% by mass or less reduces attachment of particles to a device after O 2 plasma irradiation, preventing contamination of the device. Furthermore, such an amount of particles generated reduces attachment of particles to a device, reducing impairment of yield in device production.
  • the weight reduction percentage after NF 3 plasma irradiation is 1.8% by mass or less, preferably 1.5% by mass or less.
  • the weight reduction percentage has no particular lower limit because it is preferably as small as possible.
  • the amount of particles generated after NF 3 plasma irradiation is 0.05% by mass or less, preferably 0.03% by mass or less.
  • the amount of particles generated has no particular lower limit because it is preferably as small as possible.
  • a weight reduction percentage of 1.8% by mass or less enables production of a seal material with better resistance to NF 3 plasma, improving the long-term durability.
  • a small amount of particles generated reduces attachment of particles to a device after NF 3 plasma irradiation, preventing contamination of the device. Furthermore, such an amount of particles generated reduces attachment of particles to a device, reducing impairment of yield in device production.
  • the compression set after aging at 300°C for 70 hours is 50% or less, preferably 45% or less, more preferably 40% or less.
  • a small compression set enables production of a seal material with better lifetime, which improves the long-term durability.
  • the resistance to O 2 plasma and the resistance to NF 3 plasma can be achieved by using a specific non-oxide ceramic filler.
  • a good compression set at high temperature can be achieved by surface-oxidizing the non-oxide ceramic filler.
  • Such a molded article can suitably be used as a sealant for semiconductor manufacturing devices requiring particularly high cleanliness, especially semiconductor manufacturing devices involving high density plasma irradiation.
  • the sealant include O-rings, square rings, gaskets, packings, oil seals, bearing seals, and lip seals.
  • the molded article can also be used for a variety of polymer products used in semiconductor manufacturing devices, such as diaphragms, tubes, hoses, a variety of rubber rolls, and belts, and can also be used for coating materials and lining materials.
  • the semiconductor manufacturing devices in the invention are not limited to devices for producing semiconductors, but generally widely include producing devices used in the semiconductor field requiring high cleanliness, such as devices for producing liquid crystal panels or plasma panels. Examples thereof include the following.
  • dry etching systems plasma etching systems, reactive ion etching systems, reactive ion beam etching systems, sputter etching systems, ion beam etching systems, wet etching systems, ashing systems
  • the molded article of the invention exhibits excellent performance as a sealant of a CVD system, a plasma etching system, a reactive ion etching system, an ashing system, or an excimer laser exposure system, for example.
  • Silicon carbide (NM-SiC available from Nanomakers, average particle size: 30 nm) was subjected to a heat treatment in a muffle furnace at 800°C for one hour under an atmospheric condition to provide a surface-oxidized silicon carbide.
  • the surface oxidation state of the surface-oxidized non-oxide ceramic was determined by ESCA using Mg as an X-ray source at 8 kv-10 mA.
  • 40% of SiC in a 3- to 5-nm surface layer was confirmed to be reduced and converted into SiO 2 while 60% of SiC was confirmed to remain as SiC (the ratio between the peak assigned to SiO 2 and the peak assigned to SiC was 2:3).
  • the NphAF used was 2,2-bis[3-amino-4-(N-phenyl amino)phenyl]hexafluoropropane.
  • the heat-treated silicon carbide used was the heat-treated silicon carbide of Production Example 1.
  • the silicon oxide used in Comparative Example 7 was "50" available from Nippon Aerosil Co., Ltd., and the surface-treated silicon oxide used in each of Comparative Examples 8 and 9 was RX50 available from Nippon Aerosil Co., Ltd.
  • the fluoroelastomer composition obtained in each of Examples 1 and 3 and Comparative Examples 1, 3, 6 to 8, and 10 was pressed at 180°C for 30 minutes to be crosslinked, and was then subjected to oven crosslinking in an oven at 290°C for 18 hours to provide a 2-mm-thick crosslinked molded article and an O-ring (size: AS-568A-214) molded article.
  • the fluoroelastomer composition obtained in each of Examples 2, 4, and 5 and Comparative Examples 2, 4, 5, and 9 was pressed at 180°C for 30 minutes to be crosslinked, and was then subjected to oven crosslinking in an oven at 200°C to 290°C for 18 hours to provide a 2-mm-thick crosslinked molded article and an O-ring (size: AS-568A-214) molded article.
  • the resulting molded articles were measured for the hardness, the compression set, and the weight reduction percentage and amount of particles generated after plasma irradiation by the following methods. Table 1 shows the results.
  • the hardness was measured in conformity with JIS K 6301.
  • An O-ring (AS-568A-214) was formed.
  • the compression set of the O-ring was measured after aging at 300°C for 70 hours and after aging at 300°C for 168 hours in conformity with JIS K6262.
  • An O-ring (size: P-24) molded article was prepared and subjected to a plasma irradiation treatment under the following conditions and the weight change before and after the irradiation was determined.
  • Plasma irradiation device ICP high-density plasma device (MODEL RIE-101iPH available from Samco Inc.) Irradiation conditions
  • Plasma irradiation device ICP high-density plasma device (MODEL RIE-101iPH available from Samco Inc.) Irradiation conditions
  • Each sample was weighed to three decimal places with an electronic analytical balance and the obtained value was rounded off to two decimal places. Three samples were used for each kind, and the average weight reduction percentage of each kind was calculated.
  • Plasma irradiation device ICP high-density plasma device (MODEL RIE-101iPH available from Samco Inc.) Irradiation conditions
  • Plasma irradiation device ICP high-density plasma device (MODEL RIE-101iPH available from Samco Inc.) Irradiation conditions

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Drying Of Semiconductors (AREA)
  • Treatments Of Macromolecular Shaped Articles (AREA)
EP24169936.2A 2017-10-18 2018-10-17 Composition élastomère réticulable et article moulé en caoutchouc fluoré Pending EP4407002A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2017201923 2017-10-18
EP18867356.0A EP3674365B1 (fr) 2017-10-18 2018-10-17 Composition élastomère réticulable et article moulé en caoutchouc fluoré
PCT/JP2018/038627 WO2019078238A1 (fr) 2017-10-18 2018-10-17 Composition élastomère réticulable et article moulé en caoutchouc fluoré

Related Parent Applications (2)

Application Number Title Priority Date Filing Date
EP18867356.0A Division-Into EP3674365B1 (fr) 2017-10-18 2018-10-17 Composition élastomère réticulable et article moulé en caoutchouc fluoré
EP18867356.0A Division EP3674365B1 (fr) 2017-10-18 2018-10-17 Composition élastomère réticulable et article moulé en caoutchouc fluoré

Publications (1)

Publication Number Publication Date
EP4407002A1 true EP4407002A1 (fr) 2024-07-31

Family

ID=66174063

Family Applications (2)

Application Number Title Priority Date Filing Date
EP24169936.2A Pending EP4407002A1 (fr) 2017-10-18 2018-10-17 Composition élastomère réticulable et article moulé en caoutchouc fluoré
EP18867356.0A Active EP3674365B1 (fr) 2017-10-18 2018-10-17 Composition élastomère réticulable et article moulé en caoutchouc fluoré

Family Applications After (1)

Application Number Title Priority Date Filing Date
EP18867356.0A Active EP3674365B1 (fr) 2017-10-18 2018-10-17 Composition élastomère réticulable et article moulé en caoutchouc fluoré

Country Status (7)

Country Link
US (3) US11753523B2 (fr)
EP (2) EP4407002A1 (fr)
JP (3) JP6927319B2 (fr)
KR (1) KR102240635B1 (fr)
CN (2) CN114456524B (fr)
TW (3) TW202536089A (fr)
WO (1) WO2019078238A1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4407002A1 (fr) * 2017-10-18 2024-07-31 Daikin Industries, Ltd. Composition élastomère réticulable et article moulé en caoutchouc fluoré
EP3974473A4 (fr) * 2019-05-20 2023-05-31 Daikin Industries, Ltd. Composition élastomère contenant du fluor et article
WO2021038424A1 (fr) * 2019-08-27 2021-03-04 3M Innovative Properties Company Compositions de fluoropolymère durcissables comprenant des particules de fluorure de métal et articles fabriqués à partir de celles-ci
JP7015418B2 (ja) * 2020-01-28 2022-02-02 エア・ウォーター・マッハ株式会社 含フッ素エラストマー組成物、およびシール材
KR20230078694A (ko) * 2020-09-28 2023-06-02 주식회사 발카 시일재 및 시일재의 제조 방법
CN117425693A (zh) * 2021-06-08 2024-01-19 三菱电线工业株式会社 未交联氟橡胶组合物、使用该未交联氟橡胶组合物制造的密封件及其制造方法
CN114230950B (zh) * 2021-12-27 2023-04-14 上海芯密科技有限公司 一种半导体设备密封件及其制备方法
CN114196146B (zh) * 2021-12-27 2023-05-12 上海芯密科技有限公司 一种半导体密封件的制备方法及应用
CN119192756B (zh) * 2024-09-23 2025-03-21 上海芯密科技股份有限公司 一种耐等离子体且低粘力的无金属全氟聚合物及其制备方法

Citations (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS584728B2 (ja) 1976-06-30 1983-01-27 ダイキン工業株式会社 含フツ素系多元セグメント化ポリマ−の製法
JPS6157324B2 (fr) 1981-10-22 1986-12-06 Daikin Kogyo Co Ltd
JPS6212734A (ja) 1985-03-28 1987-01-21 Daikin Ind Ltd 新規フルオロビニルエ−テルおよびそれを含む共重合体
JPS6234324A (ja) 1985-08-07 1987-02-14 Hitachi Maxell Ltd 磁気記録媒体
JPH0259177B2 (fr) 1982-12-02 1990-12-11 Ii Ai Deyuhon De Nimoasu Ando Co
JPH04505341A (ja) 1989-05-19 1992-09-17 イー・アイ・デユポン・ドウ・ヌムール・アンド・カンパニー ヨウ素硬化部位を有するブロモ含有パーフルオロポリマー類の製造
JPH0481608B2 (fr) 1983-06-23 1992-12-24 Ii Ai Deyuhon De Nimoasu Ando Co
JPH05500070A (ja) 1989-05-19 1993-01-14 イー・アイ・デユポン・ドウ・ヌムール・アンド・カンパニー ヨウ素硬化部位を有するシアノ含有パーフルオロポリマー類
JPH0513961B2 (fr) 1985-03-28 1993-02-23 Daikin Ind Ltd
JPH07316234A (ja) 1994-05-18 1995-12-05 Ausimont Spa Ｏリングの製造に特に適した新規の過酸化物硬化性のフッ化エラストマー
JPH08120146A (ja) 1994-10-21 1996-05-14 Nippon Mektron Ltd 含フッ素エラストマー組成物
WO1997024381A1 (fr) 1995-12-28 1997-07-10 Daikin Industries, Ltd. Copolymeres elastiques contenant du fluor, composition durcissable les contenant et materiau d'etancheite prepare a l'aide de ces copolymeres
WO2005017017A1 (fr) 2003-08-15 2005-02-24 Dupont Dow Elastomers L.L.C. Composition de perfluoroelastomere durcissable
JP2012509975A (ja) 2008-12-29 2012-04-26 ダイキン工業株式会社 架橋性含フッ素エラストマー組成物および該組成物から作製された成形品
US8173727B2 (en) * 2001-12-17 2012-05-08 Daikin Industries, Ltd. Crosslinkable elastomer composition and molded article using the same

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT278571B (de) * 1967-12-01 1970-02-10 Kempten Elektroschmelz Gmbh Verfahren zur Herstellung von Schleifwerkzeugen
JPS5551774A (en) * 1978-10-06 1980-04-15 Kyoto Ceramic Composition and method for metallizing nonnoxide ceramic body
JPS6311572A (ja) * 1986-07-02 1988-01-19 日本鋼管株式会社 非酸化物セラミツク粉体の精製方法
JPH02199075A (ja) * 1989-12-15 1990-08-07 Toshiba Corp セラミックス―金属接合体
DE4113853A1 (de) * 1991-04-27 1992-10-29 Karl Dipl Chem Dr Elbel Verfahren zur herstellung von schleifkoerpern fuer den formfolgenden schliff
IN186662B (fr) * 1997-09-08 2001-10-20 Grindwell Norton Ltd
JP3303915B2 (ja) 1999-11-04 2002-07-22 ダイキン工業株式会社 半導体製造装置用エラストマー成形品および架橋性フッ素系エラストマー組成物
CN100366681C (zh) * 2003-01-10 2008-02-06 大金工业株式会社 交联性弹性体组合物及该交联性弹性体组合物所形成的成型品
WO2005040783A1 (fr) * 2003-10-22 2005-05-06 Ambri Limited Nouvelle configuration de capteur
JP4475973B2 (ja) * 2004-02-12 2010-06-09 株式会社トクヤマ 無機フィラー、およびその製造方法
JP4600393B2 (ja) * 2004-02-26 2010-12-15 ダイキン工業株式会社 含フッ素エラストマー組成物
CN100455624C (zh) * 2006-04-20 2009-01-28 上海道氟化工科技有限公司 氟橡胶组合物及其成型制品
JP2011213540A (ja) 2010-03-31 2011-10-27 Covalent Materials Corp シリコン含浸炭化ケイ素セラミックス及びその製造方法
US20110319545A1 (en) 2010-06-25 2011-12-29 E.I. Du Pont De Nemours And Company Process for preparing curable perfluoroelastomer compositions
JP2012106888A (ja) 2010-11-18 2012-06-07 Shinano Denki Seiren Kk 高絶縁性炭化ケイ素粉体及び該粉体を含有する組成物
WO2013172334A1 (fr) * 2012-05-15 2013-11-21 日本ゼオン株式会社 Composition conductrice
EP2930202B1 (fr) * 2012-12-04 2020-03-25 Nissin Kogyo Co., Ltd. Substance composite en fibres de carbone, et procédé de production de ladite substance composite en fibres de carbone
WO2016043100A1 (fr) * 2014-09-16 2016-03-24 ダイキン工業株式会社 Composition de fluoroélastomère et article moulé
CN106084297A (zh) 2016-06-08 2016-11-09 浙江克莱恩纳米材料股份有限公司 基于富勒烯材料的微米碳化硅微晶须复合材料及制备方法及衍生材料
EP4407002A1 (fr) * 2017-10-18 2024-07-31 Daikin Industries, Ltd. Composition élastomère réticulable et article moulé en caoutchouc fluoré

Patent Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS584728B2 (ja) 1976-06-30 1983-01-27 ダイキン工業株式会社 含フツ素系多元セグメント化ポリマ−の製法
JPS6157324B2 (fr) 1981-10-22 1986-12-06 Daikin Kogyo Co Ltd
JPH0259177B2 (fr) 1982-12-02 1990-12-11 Ii Ai Deyuhon De Nimoasu Ando Co
JPH0481608B2 (fr) 1983-06-23 1992-12-24 Ii Ai Deyuhon De Nimoasu Ando Co
JPS6212734A (ja) 1985-03-28 1987-01-21 Daikin Ind Ltd 新規フルオロビニルエ−テルおよびそれを含む共重合体
JPH0563482B2 (fr) 1985-03-28 1993-09-10 Daikin Ind Ltd
JPH0513961B2 (fr) 1985-03-28 1993-02-23 Daikin Ind Ltd
JPS6234324A (ja) 1985-08-07 1987-02-14 Hitachi Maxell Ltd 磁気記録媒体
JPH05500070A (ja) 1989-05-19 1993-01-14 イー・アイ・デユポン・ドウ・ヌムール・アンド・カンパニー ヨウ素硬化部位を有するシアノ含有パーフルオロポリマー類
JPH04505345A (ja) 1989-05-19 1992-09-17 イー・アイ・デユポン・ドウ・ヌムール・アンド・カンパニー ヨウ素硬化部位を有するシアノ含有パーフルオロポリマー類の製造
JPH04505341A (ja) 1989-05-19 1992-09-17 イー・アイ・デユポン・ドウ・ヌムール・アンド・カンパニー ヨウ素硬化部位を有するブロモ含有パーフルオロポリマー類の製造
JPH07316234A (ja) 1994-05-18 1995-12-05 Ausimont Spa Ｏリングの製造に特に適した新規の過酸化物硬化性のフッ化エラストマー
JPH08120146A (ja) 1994-10-21 1996-05-14 Nippon Mektron Ltd 含フッ素エラストマー組成物
WO1997024381A1 (fr) 1995-12-28 1997-07-10 Daikin Industries, Ltd. Copolymeres elastiques contenant du fluor, composition durcissable les contenant et materiau d'etancheite prepare a l'aide de ces copolymeres
US8173727B2 (en) * 2001-12-17 2012-05-08 Daikin Industries, Ltd. Crosslinkable elastomer composition and molded article using the same
WO2005017017A1 (fr) 2003-08-15 2005-02-24 Dupont Dow Elastomers L.L.C. Composition de perfluoroelastomere durcissable
JP2012509975A (ja) 2008-12-29 2012-04-26 ダイキン工業株式会社 架橋性含フッ素エラストマー組成物および該組成物から作製された成形品

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
G. H. KALB ET AL., ADVANCES IN CHEMISTRY SERIES, vol. 129, 1973, pages 13
KIM YOUNG-WOOK ET AL: "Sinterability of Nano-Sized Silicon Carbide Powders", JOURNAL OF THE CERAMIC SOCIETY OF JAPAN, vol. 114, no. 8, 1 January 2006 (2006-01-01), JP, pages 681 - 685, XP055877762, ISSN: 0914-5400, Retrieved from the Internet <URL:https://www.jstage.jst.go.jp/article/jcersj/114/1332/114_1332_681/_pdf/-char/en> DOI: 10.2109/jcersj.114.681 *
KOBUNSHI RONBUNSHU, JAPANESE JOURNAL OF POLYMER SCIENCE AND TECHNOLOGY, vol. 49, no. 10, pages 1992
SHIMODA KAZUYA ET AL: "Surface properties and dispersion behaviors of SiC nanopowders", COLLOIDS AND SURFACES A : PHYSIOCHEMICAL AND ENGINEERINGS ASPECTS, ELSEVIER, AMSTERDAM, NL, vol. 463, 22 September 2014 (2014-09-22), pages 93 - 100, XP029083089, ISSN: 0927-7757, DOI: 10.1016/J.COLSURFA.2014.09.013 *

Also Published As

Publication number Publication date
EP3674365B1 (fr) 2024-06-19
US20200332081A1 (en) 2020-10-22
JPWO2019078238A1 (ja) 2020-07-02
CN111212874B (zh) 2022-03-04
TWI798274B (zh) 2023-04-11
US12286523B2 (en) 2025-04-29
TW201927880A (zh) 2019-07-16
JP6927319B2 (ja) 2021-08-25
WO2019078238A1 (fr) 2019-04-25
US20250171614A1 (en) 2025-05-29
JP2021176975A (ja) 2021-11-11
JP7713826B2 (ja) 2025-07-28
EP3674365A4 (fr) 2021-05-26
JP2023134557A (ja) 2023-09-27
EP3674365A1 (fr) 2020-07-01
US11753523B2 (en) 2023-09-12
TW202330771A (zh) 2023-08-01
TWI885340B (zh) 2025-06-01
CN111212874A (zh) 2020-05-29
TW202536089A (zh) 2025-09-16
CN114456524B (zh) 2023-08-11
KR20200042920A (ko) 2020-04-24
US20230357535A1 (en) 2023-11-09
CN114456524A (zh) 2022-05-10
KR102240635B1 (ko) 2021-04-15

Similar Documents

Publication Publication Date Title
US12286523B2 (en) Crosslinkable elastomer composition and fluororubber molded article
JP5487584B2 (ja) 架橋性エラストマー組成物および該組成物からなる成形品
EP3309214A1 (fr) Composition comprenant un fluoropolymère et article moulé
JPWO2005082998A1 (ja) 含フッ素エラストマー組成物
JP2023154427A (ja) 組成物および架橋物
US12304984B2 (en) Composition containing fluorine-containing polymer and crosslinked article
JP4086070B2 (ja) 架橋性エラストマー組成物および該架橋性エラストマー組成物からなる成形品
JP7623604B2 (ja) フルオロポリマー、水性分散液、組成物および架橋物
US20250340727A1 (en) Polymer blend, crosslinkable composition and article

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20240412

AC Divisional application: reference to earlier application

Ref document number: 3674365

Country of ref document: EP

Kind code of ref document: P

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

P01 Opt-out of the competence of the unified patent court (upc) registered

Free format text: CASE NUMBER: APP_973/2025

Effective date: 20250108